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Patented Dec. 4, 1962
1
2
3,967,105
ticles are stable and they are especially characterized by
their greatly enhanced biological availability and/or ef
fectiveness.
As a preliminary step to carrying out the present in
VITAMIN (IQMPOSETHUIQJS AND PROCESSES FOR
_
3,%l,l05
PRGDUCHNG SAME
Herman D. Ratish, Flushing, N.Y., and Melvin Hochberg,
Livingston, N.J., assignors to Nopco Chemical Com
pany, Harrison, N.J., a corporation of New Jersey
No Drawing. Filed Sept. 22., 1959, Ser. No. 841,463
6 Claims. (Cl. 167—81)
vention, a protein material, namely, zein, is dissolved in
asuitable organic solvent. Normally, this will be accom
plished at or around ordinary room temperatures simply
by adding the zein to, and mixing it with, an appropri
ate unheated solvent. If desired, the preparation of the
vention relates to vitamin-containing compositions, in the
form of discrete free-?owing particles, which are charac
terized both by their stability and ‘by their enhanced bio
zein solution can be facilitated somewhat by heating the
solvent either prior to or after the addition of zein. Gen
erally, however, when an elevated temperature is used in
producing the solvent solution of zein, temperatures not
exceeding about 60° C will be employed.
particles, are well known in the art. Moreover, the suita
bility of such products for use in the production of foods,
vessel, of a mixture comprising (1) the fat-soluble vita
min material and (2) the carrier and, in certain embodi
This invention relates, in general, to new and improved
vitamin-containing products. More particularly, the in
A further step, also preliminary to the actual practice
15
logical availability and/or effectiveness.
of the invention, involves the preparation, in a separate
Vitamin-containing products, in the form of discrete
in the preparation of pharmaceutical tablets and powders
for human consumption, in the formulation of poultry
and animal foods and feeds, etc. is widely acknowledged.
In recent years, extensive research has been carried out
in connection both with vitamin-containing products, in
cluding their production, and with the uses thereof. In
general, the art has been seeking to furnish a product,
which can be produced readily in large scale quantities
and which is capable of providing vitamins in a form
in which they are stable, but yet completely biologically
ments of the invention (3) an effective antioxidant. The
methods by which this mixture is prepared will be dis
cussed fully hereinafter. After these preliminary opera
tions have been completed, the mixture comprising (1)
the vitamin material and (2) the carrier and, in those in
stances in which it is used, (3) the antioxidant is added
25 to, and suspended in, the aforementioned organic solvent
solution of zein. The stable and available vitamin-con
taining compositions of our invention are obtained sub
sequently by converting the liquid product, referred to
herein for convenience as a suspension, into dry, solid
jective has been sought to be achieved by coating the 30 particles. Neither the manner in which the aforemen
tioned suspension is produced, nor the method by which
vitamin or vitamins with, or somehow incorporating the
the solid particles are obtained therefrom, constitutes a
vitamin or vitamins into, some suitable protective media.
available and/or ecective.
For the most part, this ob
Gelatin is perhaps one of the best ‘known of the various
media heretofore utilized in the preparation of such prod
critical limitation on the practice of this invention.
In
disadvantages.
the protein, or vice versa, accompanied by efficient mix
ing. This operation will be facilitated by the use of some
mechanical means of agitation and, hence, some stirring
general, completely satisfactory results will be obtained
ucts. However, even the use of gelatin is not devoid of 35 merely by adding the mixture to the solvent solution of
One of the most serious objections to
the use of gelatin is the fact that great care must be ex
ercised in the drying of gelatin-type products. To mini
or mixing device will be utilized in the preferred practice
mize the possibility of the destruction of the vitamins
therein, the product must be dried under strictly con 40 of the invention. A suitable suspension can be prepared
by vigorous manual stirring. However, for obvious rea
trolled humidity conditions. The necessity of having to
sons, manual stirring is neither practical or ef?cient. Fur
use rigid drying controls increases both equipment and
thermore, there are various methods by which our prod
production costs. Moreover, equipment failure or hu
ucts can be obtatined from the suspension in the desired
man error during the drying operation could easily re
dry, particulate form. These methods will be described
sult in complete or partial loss of a batch. ‘Furthermore,
under conditions of high humidity, gelatin-type products
are often far less stable than is desirable.
0n the other
hand, certain prior art products, which employ a pro
tective media other than gelatin, have been found to be
far less biologically available than is desirable. Improve
ments in all of the foregoing respects, and, particularly,
in the biological availability and/or effectiveness of such
products, are still considered to be possible and are con
stantly being sought.
It is the object of this invention to provide dry, vita
min-containing compositions in the form of free-?owing,
discrete particles.
fully hereinafter.
Zcin which is employed in the formation of our novel
compositions is a commercially available protein extract
ed from corn gluten. It is, a naturally occurring high
polymer, having a probable molecular weight within the
range of 20,000 to 30,000, composed of a number of
amino acid residues bound by peptide linkages. As in
dicated heretofore, zein is dissolved in some suitable or
ganic solvent in an operation which is preliminary to the
In the production of our prod
ucts one may use any organic solvent, either anhydrous
or aqueous, provided, however, that zein is soluble there
55 practice of our invention.
1n. Preferably, however, low molecular weight, aliphatic,
monohydric alcohols, such as, methyl alcohol, ethyl alco
discrete particles, are both stable and biologically avail 60 hol and isopropyl alcohol, are used. Among the anhy
drous alcohols, only methyl alcohol is a true solvent for
able and/ or effective.
zein. Anhydrous methyl alcohol is used in the preferred
Other objects of the invention will be obvious and they
it is a further object of the invention to provide dry,
vitamin-containing compositions which, in the form of
practice of the invention. Suitable also, however, are
will, in part, appear hereinafter.
commercial aqueous ethyl alcohol (95%) and commercial
It has been discovered, that, when an intimate mixture
comprising (1) a fat-soluble vitamin material and (2) a 65 aqueous isopropyl alcohol (91%). Moreover since zein
is soluble in aqueous ethyl and isopropyl alcohols con
carrier, the nature of which will be described hereinafter,
taining as much at 40% of water by volume, such aqueous
and in certain embodiments of the invention, (3) an ef
alcohols can also be used in the practice of the invention.
fective antioxidant, is added to, and mixed with, in an
organic solvent solution of a protein material, products
The concentration ofvthe solvent solution of zein which
can be obtained from the suspension, thus obtained, in 70 is used in the practice of the invention is not, in and of
the form of discrete, free-flowing particles. These par
itself, critical. The concentration of that solution, how
3,067,105
A
is
A
ever, is a factor which has particular signi?cance in de
termining the technique or method which will be best
suited for use in the production of our products in par
ticulate form. The manner in which the concentration
of the zein solution bears upon the technique or method
to be used in producing our products will, however, be
discussed more fully hereinafter. It may be noted at
this point, however, that we prefer to employ a solution
containing a ratio of from about 2 to about 6 parts by
weight of solvent for each part by weight of zein.
In carrying out our invention, any of the natural or
synthetically produced fat-soluble vitamins, that is, vita
mins A, D, E or K, can be used. To a great extent, how
ever, the invention will be concerned with compositions
the term “edible” is used to denote a material which may
be eaten by humans and animals, in the amount in which
they are present in the products of the invention, Without
any deleterious effect resulting therefrom. By “effective
antioxidant” We mean an antioxidant capable of exerting
an antioxidizing in?uence on the vitamins in connection
with which it is used. While an effective antioxidant will
be used in the preferred embodiment of the invention,
for example, where vitamin A, or a mixture containing
vitamin A, is in use, where a less sensitive vitamin, such
as, vitamin D, is the sole vitamin ingredient of the prod
uct, the use of the antioxidant may be dispensed with.
Suitable for use in the practice of the invention are edible
antioxidants, such as, propyl gallate, butylated hydroxy
containing either vitamin A or vitamin D or mixtures 15
anisole, butylated hydroxy toluene, gallic acid, nordihy
thereof. Thus for example, activated sterols, such as,
ergosterol or irradiated 7-dehydrocholesterol, vitamin A
droguariaretic acid, ascorbyl palmitate, etc. and mixtures
in alcohol form, vitamin A produced by synthetic methods,
of these. In addition to these compounds, however, one
may use other edible antioxidants, as, for example, vita~
?sh oils, ?sh liver oils, vitamin concentrates prepared from
min B, mixed tocopherols and natural antioxidants of the
such oils, etc. can be used in producing our novel prod 20 types disclosed and claimed in US. Patents Nos. 2,345,576,
ucts. Vitamin A in ester form can be used also but we
2,345,578, 2,433,593 and 2,434,790. Natural antioxi
have found, for example, that far more satisfactory prod
dants of the type which are produced by the processes
ucts are obtained where vitamin A palmitate rather than
disclosed and claimed in US. Patents Nos. 2,396,680 and
vitamin A acetate is used. Moreover, precursors of vita
2,396,681 as well as other similar edible antioxidants, can
min A, such as, carotene, can be used in the production 25 be employed also. Mixtures of such antioxidants can be
of our products in place of vitamin A, if desired. Those
used, if desired. In fact, a mixture comprising butylated
vitamin compositions of our invention which contain
hydroxy anisole, butylated hydroxy toluene and ascorbyl
vitamin A, will have a potency of at least about 1,000
palmitate is used in producing the preferred products of
U.S.P. units of vitamin A per gram. Generally, the vita
the invention.
min A products of the invention will contain at least about 30
The quantities of the various ingredients used in pre
30,000 U.S.P. units of vitamin A per gram and, preferably,
paring our novel products can be varied within certain
between about 100,000 to 500,000 U.S.P. units of vita
limits. Thus, for example, the amount of zein which
is used in preparing the dry discrete particles of our in
vention which contain only vitamin D, will have a potency
vention may be varied. In general, the mixture of the
of at least about 10,000 U,S.P. units of vitamin D per 35 vita-min material, carrier and antioxidant will be added
gram and, preferably, about 100,000 U.S.P. units of vita
to an organic solvent having dissolved therein a quantity
min D per gram or higher.
of zein su?icient to provide from about 1.0 part to about
In general, any one of many products may be used in
3.0 parts by weight of zein for each part by weight of the
the practice of this invention as the so-called “carrier.”
fat-soluble, vitamin material. Furthermore, and as in
As used herein the term carrier is employed to denote 40 dicated heretofore, from about 2 parts to about 6 parts
hydrophilic compounds which are organic in nature and
by weight of solvent for each part by weight of zein will
which, when employed as disclosed herein, contribute
be used in carrying out our invention. Moreover, one
greatly both to the stability and the biological availability
may use from about 0.5 to about 1.5 parts by weight of
and/ or effectiveness of the product. Suitable for use as
carrier for each part by weight of vitamin material em
the carrier are synthetic polysaccharides; natural gums,
ployed. Finally, when used, the antioxidant, or the
such as, guar gum; normally solid polyethylene glycols;
antioxidant mixture, will comprise from about 0.5% to
normally solid fatty acids, such as, palmitic acid, stearic
about 12.0% of the total weight of the ingredients in the
acid, etc.; sorbitol powder; glyceryl monostearate; pectins;
vitamin, carrier and antioxidant mixture.
min A per gram. Those vitamin compositions of our in~
starch; starch dextrins; non-fat dry milk; and mixtures
of two or more of these.
Well suited for use are syn
thetic polysaccharides sold by Corn Products Co., New
As has been indicated heretofore, a mixture of the
vitamin material, and the carrier, and, optionally, the
York, New York under the trade-name Polyose. These
antioxidant, is produced in a step preliminary to the
actual practice of the invention. The most satisfactory
are powdery products, produced by the controlled and
catalyzed polymerization of special corn sugars, which
method for accomplishing this, in any given instance, will
be determined, for the most part, by the properties of
are soluble in water and insoluble in organic solvents.
They are available commercially under the trade-names
carrier in use. For example, Where the surface character
istics of carier used are such that the addition of the
vitamin-containing material thereto will result in the ad
herence of the vitamin material to the surface of the car
Polyose A, Polyose B, Polyose C and Polyose D. Nor
mally solid polyethylene glycols which have been found
to be especially well suited for use are sold under the
rier, a suitable mixture will be obtained by completely
trademark Carbowax by Carbide and Carbon Chemicals
and thoroughly mixing those ingredients. This mixing
60
Company, New York, New York. Carbowax 4000 (aver
operation can be accomplished either at room temperature
age molecular weight of 3000 to 3700 and a freezing
or at a temperature which is elevated somewhat above
range of 53° C. to 56° C.) and Carbowax 6000 (average
room temperature. Ordinarily, when this technique or
molecular weight of 6000 to 7500 and a freezing range
procedure is utilized, and an antioxidant is to be employed,
of 60° C. to 63° C.) are used in certain preferred em
the antioxidant will be provided in the form of a solvent
bodiments of the invention. In addition, mixtures of 65 solution thereof. In the case of butylated hydroxy ani
synthetic polysaccharides, such as, the various Polyose
products, with the various Carbowax products are suit
able for use. The other carriers mentioned heretofore, or
sole, butylated hydroxy toluene and ascorbyl palmitate,
the antioxidants used in preparing the preferred products
of the invention, methyl alcohol is generally used as the
rnixturesof two or more of such carriers, can be used
solvent therefor. Any other solvent for the antioxidant
Moreover, such other carriers can be used in 70 or ‘antioxidants in use which is compatible with the vari
alone.
admixture with Polyose products or Carbowax products
ous zein solvents can be used in place of methyl alcohol,
or in admixture with a combination thereof.
_
An edible and effective antioxidant can be, and is pref
erably used in the practice of this invention. As used
however. Where the carrier is a Polyose product, the
foregoing will be found to be an entirely suitable method
throughout the present speci?cation and in the claims, 75 for preparing the mixture. The mixing of the ingredients
v3,067,105
.
v
.
..
5
5
is carried out, generally, using some ef?cient mechanical
means. Where, however, a carrier, such as, a Carbowax
product, a pectin, palmitic acid, stearic acid, etc. is to be
used, somewhat modi?ed methods for producing the de
sired mixture will be found to be more satisfactory.
When, for example, a normally solid polyethylene glycol
described conditions, by the time that the droplets have
completed their free ?ight through the air and have come
to rest on the ?oor, they will have become substantially
solidi?ed. Using this centrifuging method, the size of
the particles of the product can be regulated by changing
the speed at which the perforated vessel is rotated. By
increasing or decreasing the speed at which the vessel is
is used, such as, a Carbowax product, or a solid fatty acid,
rotated, one can decrease or increase, respectively, the
such as, stearic acid or palmitic acid or where glyceryl
size of the particles obtained. Moreover, adjustment in
monostearate is in use, one can proceed by ?rst heating
the carrier to a temperature above its melting point. The 10 the size of the particles can be accomplished by increasing
or decreasing the amount of organic solvent which is used.
vitamin material and, if it is to be used, the antioxidant
As a general rule, particles of larger size will be obtained
are subsequently added to the molten mass and mixed
from a more highly concentrated suspension.
therein. On cooling, a completely satisfactory mixture
An alternative method for obtaining our product in
will have been obtained. Where, however, the carrier in
use is pectin, starch, starch dextrin, sorbitol powder, non 15 the form of discrete particles has been found to be satis
factory where a lesser quantity of solvent is used initially
fat dry milk or a natural gum, such as, guar gum, the car
in preparing the zein solution. Such would be the case
rier can be added to a relatively small quantity of suitable
where the zein solution which ‘was employed originally in
solvent, for example, water or a water-alcohol mixture,
producing the suspension contained about 3 parts by
‘and the vitamin material and, optionally, the antioxidant
added thereto and intimately admixed therewith. This .20 weight of solvent for each part by weight of zein. This
procedure involves pouring the suspension onto a suitable
solvent procedure can, of course, be used also when the
carrier employed is a Carbowax product, a normally solid
fatty acid, glyceryl monostearate, etc., however, where
such a carrier is in use, it is preferred to prepare the de
sired mixture by the melt method rather than by the
solvent method. The mixture, in solvent, is used as such
in the practice of the invention. For this reason, the
solvent used in preparing the desired mixture should be
one which is compatible with zein solvent. The mixture
prepared by any one of the foregoing methods or obvious
equivalents thereof, is added to, and mixed with, the
organic solvent solution of zein to produce the suspension
from which our products are prepared.
In general, any one of several procedures or techniques
can be utilized to convert the aforementioned suspension
into the desired dry, discrete particles.
Obviously, the
quantity of solvent which is used at the outset in produc
ing the zein solution will be largely determinative of the
fluidity of the suspension ultimately obtained. The ?uidity
of the suspension, in turn, will have considerable bearing
on the selection of the procedure which will be most ef
fective in converting the suspension into the discrete
vitamin-containing particles of our invention. As indi
cated heretofore, we prefer to employ a zein solution con
surface, as, for example, a stainless steel plate or con
veyor, spreading it thinly over the plate or conveyor and
permitting the solvent to evaporate under normal atmos
pheric conditions. Removal of the solvent can be facili
tated by blowing air or nitrogen gas over the surface of
the ?lm. Carrying out the procedure in a heated room,
for example, in a room heated to about 100° F. obviously,
will, increase the rate at which the solvent is volatilized.
When all of the solvent has been volatilized, the dry ?lm
is removed from the plate or conveyor by any convenient
or appropriate means, for example, a doctor blade, and
subsequently reduced to particles of desired size by means
of the use of some suitable grinding or pulverizing appara
tus.
Another method for preparing our product in the form
of dry discrete particles will be found to be particularly
effective where an even more concentrated solution of
zein, for example, a solution containing 2 parts by weight
of solvent for each part of zein, is used at the outset.
This procedure involves pouring the suspension into a
suitable vessel containing a relatively large amount of
crushed ice. The suspension is mixed vigorously therein
while the temperature is maintained at about 15° C., or
lower, ‘and, preferably at about 5° C. A ?ne powdery
product, which settles out to the bottom of the container,
is formed by this procedure. When the ice has melted
an organic solvent solution of zein has been used which
and the powder has completely settled, the water may be
is relatively dilute insofar as the zein constituent is con
either siphoned off by suitable means or the powdery prod
cerned, as, for example, where the solution comprises
from 4 to 6 parts by weight of solvent for each part by 50 uct may be separated therefrom by ?ltration. The pow
taining a ratio of from about 2 parts to about 6 parts by
weight of solvent for each part by weight of zein. When
weight of zein, a highly satisfactory method for obtaining
our products in the form of discrete particles involves the
use of a rapidly rotating, perforated, stainless steel vessel,
for example, stainless steel cup, which is elevated above
floor level. While the height of this vessel above floor 55
level can be varied, we have found that best results are
obtained when the vessel is elevated at least about 15 feet
above the ?oor land is centered in a room or chamber at
dery product thus obtained is subsequently dried under
vacuum.
Other methods for obtaining our products in
the form of discrete particles will be immediately‘ appar
ent to those skilled in the art. One other such process is
a spraying procedure such as is disclosed in US. Patents
2,777,797 and 2,777,798.
Many advantages ?ow from the practice of our inven
tion. By it, one can obtain vitamin compositions in the
form of dry free-?owing particles. These products will
least about six to eight feet from each wall. The suspen
be
found to possess a very high degree of stability. Un
60
sion is poured into this rotating vessel and our product, in
der conditions of high humidity, a situation often en
the form of liquid droplets, will be centrifuged out of,
countered either in the storage of the products themselves
and away from, the vessel. To facilitate the removal of
or in the storage of feed supplemented therewith, these
the volatile solvent, this operation is preferably carried
products are superior in stability to the conventional
Moreover, our products will be
found to be readily available and/ or eifective biologically.
The high stability and biological availability and/ or eifec
tiveness of the products of this invention will render them
well'suited for use in the formulation of animal and poul
out in a heated room ‘or chamber, for example, in a room
or chamber heated to a temperature of about 100° F. 65 gelatin-type products.
The volatization of the solvent can be expedited also,
however, simply by heating the suspension to a tempera
ture of about 100° F. prior to pouring it into the per
forated cup and by providing some effective means, for
try feeds, in the preparation of pharmaceutical tablets
example, a blower, to facilitate the removal of the sol 70
and powders and in the production of food for human
vent vapor from the chamber. However, by increasing
consumption. A particular-1v outstanding feature of the
the height of the fall of the particles and by maintaining
invention resides in the fact that certain properties thereof
the room or chamber below the saturation point of the
render our products highly satisfactory for use in particu
solvent, the production of the solid particles can be ac
complished at ordinary room temperatures. Under the 75 lar commercial applications. For example, our products
3,067,105
7
53:
have great utility in the pelleting of stock and poultry
Discrete liquid droplets were centrifuged out of, and away
from, the spinning cup. By the time that they had com
pleted their free flight through the air, these liquid droplets
feed and in the production of vitamin forti?ed animal
foods, such as, cooked dog foods. In pelleting, ideal
steam application will raise the meal temperature to from
had substantially solidi?ed to form small sized, discrete
180° F. to 190° F. and the feed will be raised to a high
moisture content. In the production of cooked dog foods,
particles, each of which were stable and readily available
and/or effective biologically.
the temperature of the mass will reach 212° F. or slightly
higher. When our products are used in those, and other
comparable, procedures, under such extreme conditions,
The Polyose D used in the above example is a white to
light tan colored powdery product produced by the con
trolled and catalyzed polymerization of special corn
the vitamin ingredients therein are not destroyed and the 10 sugars. It is soluble in water and insoluble in organic
biological availability and/ or effectiveness thereof is not
solvents. In the form of a 10% aqueous solution it has a
impaired. In addition, our products are extremely well
pH of not less than 3.5 and in the form of a 40% solids
suited for use in the production of pharmaceutical tablets.
solution in water it has a viscosity of 20‘ to 1001 poises
No deterioration or destruction of vitamins in our prod—
at 70° vF.
ucts occurs during the conventional tablet compression 15
Example II
procedures. Moreover, the vitamins in our products are
In this example, an alternate method for producing our
stable even in the presence of compounds in the tablets,
products in the form of dry, solid particles was employed.
for example, minerals, which, under ordinary circum
stances, exert an adverse or deleterious effect on vitamins.
Our invention is noteworthy also in that, while it provides
easily handled products having outstanding stability prop
erties and enhanced biological availability and/or effec
tiveness characteristics, the procedure by which these
The ingredients, and the quantities thereof, which were
used in Example I were used herein except that, in this
example, 150 ml. of anhydrous methyl alcohol was em—
ployed in producing the zein solution instead of the 300
ml. used in the previous example. The procedures used
in this example in preparing the zein solution and mixture
products are obtained is quite economical in its operation
and readily adaptable for use in the production of the 25 of vitamin material, carrier and antioxidant were the same
as those employed in Example I.
products in commercial quantities. For example, the
The product in the form of discrete particles was ob
utilization of rigid humidity controls such as characterize
tained as follows: A suspension of the mixture of the
the production of gelatin-type products is obviated by our
vitamin material, carrier and antioxidant in the zein solu
invention. Moreover, although mild external heating can
tion was ?rst prepared by the procedure described in Ex
be utilized in certain stages of the procedure to facilitate
ample I. The suspension thus obtained was poured onto
the preparation of our products, the fact that our products
a stainless steel plate and, with the aid of a doctor blade,
can be produced at relatively low temperatures, for ex
ample, at temperatures at or near room temperature, is a
further feature of the invention.
For a fuller understanding of the nature and objects
of this invention, reference may be had to the following
examples which are given merely as further illustrations of
it was spread to form a thin layer, that is, a layer of about
0.007 inch, over the surface of the plate. It was allowed
to dry at ordinary room temperature. When the solvent
had completely evaporated, the thin, brittle ?lm, thus
formed, was removed from the plate and reduced to dis
crete particles by means of the use of a grinding apparatus.
The product, thus produced, was stable and biological
sense. All parts given in the examples are parts by
ly available and/ or effective.
weight, unless otherwise indicated.
40
the invention and are not to be construed in a limiting
Example [11
Example I
This example is directed to a third method for produc
To exemplify one of the several methods by which the
products of this invention are prepared, the following pro
ing our novel products. The ingredients employed here
cedure was carried out: Fifty parts of zein were ?rst
in, and the quantities thereof used, were the same as those
added to, and dissolved, in 300 ml. of anhydrous methyl
alcohol. The dissolution of the zein in the methyl alcohol
was accomplished while the alcohol was at a temperature
of 60° C.
'
In a separate vessel 30 parts of butylated hydroxy
anisole, 1.5 parts of butylated hydroxy toluene and 1.5
parts of ascorbyl palmitate were dissolved in 10 ml. of
methyl alcohol. To this solution, 25.0 parts of vitamin
A palmitate havin0 a potency of 1,000,000 U.S.P. units
of vitamin A per gram were added.
This mixture was
agitated, at high speed, using a mechanical stirrer. A cur
rent of nitrogen gas was passed, continuously during the
stirring, over the opening of the vessel in which the mix
used in Example I, except that, in this example, 100 ml.
of anhydrous methyl alcohol were used in place of the 300
‘ml. thereof employed in Example I. The. 'procedures
used in this example both in the preparation of the zein
solution and in the preparation of the mixture ‘of the
vitamin material, carrier and antioxidant were the same
as those employed in Example I.
The product, in the form of discrete particles, was ob
tained as follows: The mixture of the vitamin material,
carrier and antioxidant was suspended in the zein solution
by the method described in Example I. Thereafter, this
ing was taking place. Thereafter, 19.0 parts of Polyose
suspension was poured slowly into a Vessel containing 500
grams of crushed ice. This mixture was then stirred at
about 3000 rpm. using a mechanical stirrer, the tem
added to the mixture and thereafter until a uniform sus
under vacuum.
pension was obtained.
The product, thus obtained, was stable and readily avail
able and/ or effective biologically.
perature during the initial stirring being maintained at
D, a synthetic polysaccharide sold by Corn Products Sales
Company, New York, New York, was added to the mix 60 about 5° C. A ?ne powdery product was formed which
tended to settle to the bottom of the vessel. The ice was
ture with stirring. Vigorous agitation was continued until
allowed to melt and, when it had melted, stirring was dis
the mixture was uniform. The solvent solution of zein
continued and the powdery product was allowed to settle
was thereafter added to the mixture while the mixture was
out. The product was separated from the Water by ?ltra
being stirred by mechanical means at 3000 rpm. Stir
tion and the residual powdery product was thereafter dried
ring was continued while the zein solution was being
.
Discrete particles were obtained from the suspension in
the following manner: In a room or chamber, the ?oor of
which was heated to a temperature of about 100° F., a 70
perforated stainless steel cup was suspended about 15 feet
above ?oor level. The metal cup was approximately 4
inches in diameter and it was attached to a high speed
motor shaft. With the cup spinning at a speed of about
5000‘ rpm, the suspension was slowly poured therein.
Example IV
In this example, 37.6 parts of zein were ?rst added to,
and dissolved, in 150 ml. of anhydrous methyl alcohol
which had been heated previously on a steam bath to a
temperature of about 60° C. Concurrently therewith,
1.6 parts of butylated hydroxy toluene, 2.8 parts of butyl
3,067,105
10
.
ated hydroxy anisole and v1.6 parts of ascorbyl palmitate
of anhydrous methyl alcohol, were added to the mix~
were dissolved, at a temperature of about 50° C., in 20.0
ture.
parts of vitamin A palmitate having a potency of 1,000,000
U.S.P. units of vitamin A per gram. To this mixture, 12.0
parts of melted Carbowax 6000‘ were added. To this,
24.0 parts of Polyose D were added with agitation. There
after, the solution of zein, which was prepared in the man
The solvent-containing mixture of vitamin material,
carrier and antioxidant was subsequently mixed vigor
ously with the solvent solution of zein. The product, in
the form of the desired discrete particles, was obtained
by the centrifuging method described in Example I.
This product was evaluated for its stability by the
ner described heretofore, was added to the mixture. Dur
method described in Example IV. It was found that
ing this step the mixture was stirred at about 3000 rpm.
Vigorous agitation was continued until a uniform suspen 10 this product, after storage in an incubator at a tempera
ture of about 37° C. for a period of one month, had
sion was obtained.
involved the storage of samples of the product in an in
retained 93% of its original vitamin A potency. More
over, it was found that the product had retained about
80% of its original Vitamin A potency at the end of three
months exposure to the atmosphere at 37° C. In the
case of the samples of this product which were stored
cubator for a period of three months at a constant tern
in an incubator at a constant temperature of about 45°
Discrete particles were obtained from the suspension by
the centrifuging method described in Example I.
The stability of the product obtained in this example
was evaluated by accelerated storage tests.
These tests
perature of 37° C. and the storage of other samples in an
incubator for a period of two months at a constant tem
perature of 45° C. Before storing same, however, the .
particles were assayed for their vitamin A content and
were found to contain an average of 200,000 U.S.P. units
of vitamin A per gram. In the case of the samples stored
at a temperature of 37° C., the product was assayed once
again after one month of storage and again after three
months storage. At the end of one month storage at 37°
C., no destruction of vitamin A had occurred. At the end
of three months storage at 37° C., the assay revealed that
the product had retained about 80% of its original vita
min A potency. In the case of the. product stored at 45° 30
C., an assay was carried out at the end of two months.
Storage at that temperature and for that period of time is
generally considered to be equivalent to storage for a
period of one year at normal temperatures.
C., assay revealed that the product retained about 74%
of its original vitamin A potency at the end of two
months.
This product was evaluated for its biological availability
and/or effectiveness by the test method described in
Example IV. In this instance, however, the chicks were
maintained on the test diet for a period of 27 days rather
than 28 days. A sampling of birds in the same lot
from which those used in this test were taken revealed
that these chicks contained an average of about 65 units
of vitamin A per total weight of liver before being placed
on the test diet.
At the end of the test period, the weight of the birds
which were fed a feed containing the product of this
example was found to have increased on the average of
238.4 grams. Each bird consumed an average of 555.95
grams, or 1.225 pounds, of feed during the test period.
Assay of the
Since the feed contained 4800 International Units of
samples stored for 2 months at 45° C. revealed that the
vitamin A per pound, the total average vitamin A in
product had retained 64% of its original vitamin potency.
take, per bird, was about 5800 International Units.
The product of this example was tested for its biological
The livers of a representative number of those birds
effectiveness and availability as follows: two separate lots
were, thereafter, assayed for stored vitamin A by the
of one day old New Hampshire Cockerel chicks, the lots
comprising 10 chicks each, were fed a basal diet to which 40 method described in Example IV. Analysis revealed
the storage of an average of 1898 International Units of
had been added the product of this example. A sampling
vitamin A in the total liver. This represented the storage
of birds in the same lot from which these were taken
of about 32.2% of the total vitamin A intake. In gen
revealed that, on the average, these chicks contained an
eral, the storage of any quantity of vitamin A above
average of about 65 units of vitamin A per total weight
20% of the total vitamin A intake indicates exceptional
of liver before being placed on the test diet. The product
availability of the vitamin source. The storage of 32.2%
of the example, on the basis of its assayed vitamin A
of the total vitamin A intake in the present instance
potency, was added to the feed in such quantities as to
demonstrates the outstanding biological availability of
provide a level of 4800 International Units of vitamin
the product of this example.
A per pound of feed. The chicks were provided with
this Vitamin supplemented \feed and with water, ad
Example Vl
libitum, for a period of 28 days. At the end of that time,
In this example( 52.0 parts of zein were ?rst added
the livers were removed from four representative birds
to, and dissolved in, 200 ml. of solution comprising 80%
in each of the two lots. The freshly removed livers
by weight of methyl alcohol and 20% by weight of
were analyzed for Vitamin A content by the method of
water. Prior to adding the zein thereto, the aqueous
Galleys and Hoefer described in Ind. Eng. Chem. (Anal.
alcohol had been heated to a temperature of 60° C.
Edition), 18, 288 (1946). The assay revealed the storage
In a separate mixing vessel, 50 ml. of a 40% methyl
of an average of 1000 International Units of vitamin
alcohol in water was added to 10.0 parts of Pectin NE.
A in the total liver.
The latter product is pectin produced by Colyer Pectin
The foregoing result demonstrated that the product of
this example possessed excellent biological availability 60 Company, New York, New York. These ingredients
were mixed until the solvent was taken up by the pectin
and/ or effectiveness characteristics.
and swelling of the pectin resulted. Mixing was con
Example V
tinued until a smooth preparation was obtained.
In this example, 54.0 parts of zein were ?rst dissolved
In another separate container, 3.0 parts of butylated
in 280 ml. of anhydrous methyl alcohol which had been
hydroxy anisole, 1.5 parts of butylated hydroxy toluene
previously heated to a temperature of 60° C.
and 1.5 parts of ascorbyl palmitate were dissolved in 5
ml. of methyl alcohol. Thereafter, 32.0 parts of vitamin
A palmitate having a potency of 1,750,000 U.S.P. unit of
In a separate vessel, 2.7 parts of butylated hydroxy
anisole, 1.35 parts of butylated hydroxy toluene and 1.35
parts of ascorbyl palmitate were mixed. This mixture
was then dissolved in 10 ml. of heated methanol. There
after, 27.0 parts of vitamin A palmitate having a potency
of 1,750,000 U.S.P. units of vitamin A were added to
the antioxidant solution and mixed vigorously therewith.
While agitation was continued, 13.5 parts of Carbowax
4000, which had been previously dissolved in 10 ml. 75
vitamin A per gram were added to, and mixed with, the
antioxidant solution.
Subsequently, the vitamin A-antioxidant mixture was
mixed with the pectin preparation heretofore described.
The mixture was stirred and heated on a steam bath at a
temperature of ‘about 60° C.
A mechanical means of
agitation was employed. Thereafter, the solution of zein
3,067,105
12.
1 l.
in aqueous methyl alcohol, prepared as described here—
tofore, was then added to that mixture. The ingredients
uated for its biological availability and/ or effectiveness by
the liver storage method set out in Example IV and the
were stirred vigorously until a uniform suspension was
product was found to possess a very high degree of bio
obtained.
The desired product, in the form of small, solid par
ticles was obtained from this suspension by the method
described in Example IV. The vitamins in this product
were found to be highly stable. Assay of samples of
logical availability and/or effectiveness.
While the test
method was the same as that described in Example IV,
the present products were evaluated using one day old
White Ventress chicks which contained an average of 65
units of vitamin A per total weight of liver before being
placed on the test diet.
At the end of this test period, the weight of the birds
three month periods, revealed that the product had re 10
which were fed a feed supplemented with the product
tained 89% and 75%, respectively, of its original vitamin
of this example was found to have increased an average
A potency. Assay of samples stored at 45° C. revealed
of 352.1 grams. Each bird consumed an average of
that the product had retained 60% of its original vitamin
745.75 grams, or 1.6426 pounds, of feed during the pe
A potency at the end of two months.
riod. Since the feed contained 4800 International Units
Moreover, the product was found to possess excellent
of vitamin A per pound, the average total vitamin A
biological availability and/or effectiveness characteristics
when evaluated by the method described in Example 1V.
intake, per bird, was about 7886 International Units.
The livers of a representative number of these birds
In this case, however, the study was conducted using
White Ventress chicks rather than New Hampshire Cock
were, thereafter, assayed for stored vitamin A by the
erel chicks. A sampling of birds from the same lot from 20 method described in Example lV. Assay revealed the
the product, after storage at 37° C. for one month and
which the chicks used in the present tests were taken
storage of an average 2285 International Units of vitamin
revealed that, before being placed on the test diet, these
A in the total liver. This represented the storage of
about 29.0% of the total vitamin A intake. Since, as indi
cated heretofore, the storage of any quantity of vitamin
contained, an average of about 65 units of vitamin A
per total weight of liver.
At the end of the 28 day test period, the weight of the
birds which were fed a feed containing the product of
this example was found to have increased an average of
about 415.6 grams. Each bird consumed an average of
A above 20% of the total vitamin A intake indicates ex
ceptional availability of the vitamin source, the storage
of 29% of the total vitamin A intake in the present in
stance demonstrated the outstanding biological availability
of the product of this example.
'
839.1 grams, or 1.848 pounds, of feed during that period.
To demonstrate that the stability of the product of this
Since the feed contained 4800 International Units of 30
invention is attributable to the combination of the ingredi
vitamin A per pound, the average total vitamin A intake,
ents comprising the products, the product of this example
per bird, was about 8870 International Units.
was compared with a product identical thereto in all
The livers of a representative number of these birds
respects, except one. The product employed for com
were, thereafter, assayed for stored vitamin A by the
parative purposes diifered from the product of the ex
method described in Example IV. Analysis revealed the
ample only in that it contained no Polyose D.
storage of an average of 2559 International Units of vita
- Su?icient quantities of the product of this example were
min A in the total liver. This represented the storage of
then added to a commercial mineral mixture in such
about 28.8% of the total vitamin intake. Since, as indi
quantities as to provide therein a level of 1000 U.S.P.
cated heretofore, the storage of any quantity of vitamin A
above about 20% of the total vitamin A intake indicates All) units of vitamin A per gram of mixture. The same type
of mixture was prepared using the comparative product.
exceptional availability of the vitamin source, the storage
Each mixture was assayed initially for vitamin A and
of 28.8% of the total vitamin A intake in the present
instance was considered to be demonstrative of the out
then stored at a constant temperature of 37° C. Samples
standing biological availability of the product of this
of each mixture were thereafter assayed for vitamin A at
example.
the end of one month, two months and three months
storage. The results of this test are set forth in the table
Example VII
which follows:
In this example, 56.3 parts of zein were ?rst added to
and dissolved in 260 ml. of anhydrous methyl alcohol.
Percent of Vitamin A
The alcohol was previously heated to a temperature of 50
about 60° C.
Potency Retained
In a separate vessel, 3.0 parts of butylated hydroxy
toluene, 1.5 parts of butylated hydroxy anisole, 1.5 parts
of ascorbyl palmitate were dissolved in 10 ml. of methyl
alcohol. To the antioxidant solution, 25.2 parts‘ of vita
min A palmitate having a potency of 1,095,000 U.S.P.
units of vitamin A per gram were added.
This mixture
was agitated vigorously and, concurrently therewith, a
current of nitrogen gas was passed over the opening at
One
Two
Three
Month Months Months
Product of Example VII ____________________ __
Comparative (No Polyose D) Product ______ __
i
90
67
G4. 5
57
34
26.2
The foregoing clearly demonstrates that the superior sta
bility of the products of this invention is attributable to
the use of a combination of zein, the carrier and the
the top of the vessel. While the mixture was being 60 antioxidant in a vitamin A product.
stirred, a solution comprising 12.5 parts of Carbowax
4000 dissolved in 10 ml. of methanol was introduced
Example VIII
therein. Thereafter, the zein solution was added to, and
mixed with, that mixture. The product, in the form of
discrete particles was obtained by the method described
in Example I.
The product, thus produced, was evaluated for its sta
In this example, 47.5 parts of zein were ?rst added to,
and dissolved in, 100 ml. of 80% methyl alcohol which
bility by the accelerated storage method described in
Example IV. The product was found to have retained
had been heated previously on a steam bath to a tempera
ture of about 60° C. Concurrently therewith, 2.9 parts
of butylated hydroxy anisole, 1.6 parts of butylated hy
100% of its original vitamin A potency at the end of
one month, and 80% of the original vitamin A potency
at the end of three months, at 37° C. Assay of samples
of the product stored at 45° C. revealed that the product
had retained 71% of its original vitamin A potency at
droxy toluene and 1.2 parts of ascorbyl palmitate, were
dissolved, using mild heat, in 20.0 parts of vitamin A
palmitate which assayed at 1,000,000 U.S.P. units of
vitamin A per gram. To this mixture, 11.7 parts of guar
gum was added. The mixture, thus obtained, was agi
tated using a high speed stirrer for a period of about
3 minutes. Thereafter, 10.0 parts of Carbowax 6000
the end of two months. Moreover, the product was eval
were melted on a steam bath and added to, and mixed
3,967,105
13
palmitate in an oil carrier.
with, the mixture using a high speed stirrer. When the
mixture was homogeneous, the zein solution, prepared as
described above, was added thereto and high speed agita
in this study, a total 36 one
day old White Ventress chicks were divided into two lots
of 18 chicks each.
Each lot was subjected to a liver
storage study substantially identical to that described in
tion was continued for 5 minutes.
the preceding examples.
The smooth ?owing preparation which was obtained
was poured onto a stainless steel plate and, with the aid
of a doctor blade, it Was spread to a film of approxi
One lot of chicks was fed a
basal diet which contained su?icient quantities of fish
liver oil to provide a level of 4800 international Units
of vitamin A per pound of feed. The chicks were pro
mately 1/50 of an inch thickness. It was allowed to dry,
vided with this supplemented feed, and with water, ad
at room temperature, to a brittle film. The brittle ?lm
was removed from the plate and it was converted to solid 10 libitum, for a period of 24 days. The second lot of
chicks were fed a basal diet which contained su?icient
particles by grinding.
quantities of synthetic vitamin A palmitate in a corn oil
carrier to provide a level of 4800 International Units of
vitamin A per pound of feed. This lot of chicks was
The product, thus obtained, was evaluated for its
stability by the accelerated storage method described in
Example IV. The product was found to have retained
90% of its original vitamin A potency at the end of one
month, and 78% of its original vitamin A potency at
the end of three months, at 37°C. Assay of samples of
the product stored at 45° C. revealed that the product
retained 73% of its original vitamin A potency at the
end of two months.
provided with this supplemented feed, and with water,
ad libitum, for a period of 24 days.
After 24 days on these regimens, the lot of chicks which
had received the feed supplemented with ?sh liver oil
had gained an average of 261.5 grams. The chicks in
this test lot had consumed an average of 1.112 pounds
of feed during the test period. Since the feed contained
4800 International Units of vitamin A per pound of feed,
this represents an average total vitamin A intake, per bird,
of about 5338 International Units of vitamin A. The
livers of a representative number of the birds in this lot
were thereafter assayed for stored vitamin A by the
method described in the Example IV. Assay revealed
the storage of 462 international Units of vitamin A in
the total liver. This represented the storage of about
8.5% of the total vitamin A intake.
The chicks in the second lot, that is, the chicks receiv
ing the feed supplemented by vitamin A palmitate in a
In its biological availability and/or effectiveness, this
product proved to be satisfactory.
Example IX
In this example, 47.5 parts of zein were ?rst dissolved
in 100 ml. of 80% methyl alcohol which had been heated
previously on a steam bath to a temperature of about 60°
C. Concurrently therewith, 2.8 parts of butylated hy
droxy anisole, 1.4 parts of butylated hydroxy toluene and
1.1 part of ascorbyl palmitate were dissolved, using mild
heat, in 23.75 parts of vitamin A palmitate which assayed
at 1,750,000 U.S.P. units of vitamin A per gram. There
after, this vitamin—antioxidant mixture was added to 23.5
parts of guar gum and mixed well therewith. Subse
corn oil carrier, had gained an average of 265.9 grams
at the end of the 24 day test period. Each chick in the
lot had consumed an average of 1.165 pounds of feed
during that period. This represented an average total
vitamin A intake, per bird, of about 5592 International
quently, the solution of zein, prepared as described here
tofore, was added to and mixed with, the vitamin-antioxi
dant guar gum mixture using high speed agitation. The
Units of vitamin A. The livers of a representative num
ber of birds in this lot were thereafter assayed for stored
product, thus obtained, was reduced to small size particles
by the method described in Example I.
vitamin A by the method described in Example IV. As
A test was conducted to evaluate the products of this
say revealed the storage of an average of 475 Interna
invention for use under conditions of high humidity. In
conducting this test, a suf?cient quantity of the product
ional Units of vitamin A in the total liver. This repre
sented the storage of about 8.5% of the total vitamin
A intake.
was added to a commercial trace mineral mixture to pro
vide a product containing a level of 1000 U.S.P. units
of vitamin A per gram. The product was initially as
sayed for its vitamin A potency.
The foregoing results, when compared with the results
reported in the previous Examples V, VI and VII, dramat
This product was
ically depict the value of the present products as means
for fortifying feeds with vitamins. The storage of 8.6%
and 8.5% of the total vitamin A intake in the case of
chicks fed feeds supplemented with fish liver oil and syn
maintained at a constant temperature of 37° C. and a
constant relative humidity of 80% for a period of one
month. Samples of the product were assayed for vitamin
A at the end of 14 days and one month storage.
For
comparative purposes, a commercially available vitamin
A in gelatin product was subject to the same test.
thetic vitamin A in a corn oil carrier, respectively, is to
be contrasted with the storage in the liver of over 28%
of the total vitamin A intake in the case of caicks fed a
The
results of these tests were as follows:
diet supplemented by the vitamin-containing products of
this invention. In the preceding Example V, the vitamin
Percent Vitamin A.
Retained
14 days
One
month
A storage in the livers of the chicks where were fed a
feed containing the product of that example amounted to
32.2% of the total vitamin A intake. In Example Vii
hereof, vitamin A storage in the livers of the chicks which
60 were fed a feed containing the product of that example
amounted to 28.8% of the total vitamin intake.
Product of Example IX _________________________ __
73
61
Gelatin-Type Product: ___________________________ __
64
44
These results clearly demonstrate that, under condi
tions of high humidity, the products of this invention are
superior in stability as compared to the ordinary gelatin
type product.
Example X
In Ex
ample Vll, vitamin A storage in the livers of chicks fed
a feed containing the product of that example amounted
to 29% of the total vitamin A intake. These results,
when contrasted with those obtained when fish oil and
vitamin A palrnitate in an oil carrier were used, clearly
indicate the greatly enhanced biological availability
and/ or effectiveness of the products of the invention.
Having described our invention, what we claim as new
For compartive purposes, and to more dramatically 70 and desire to secure by Letters Patent is:
demonstrate the greatly enhanced biological availability
and/or effectiveness of the products of this invention, a
liver storage study was conducted on chicks which were
fed a feed supplemented with conventional sources of
vitamin A, namely, fish liver oil and synthetic vitamin A 75
1. Stable and biologically available and effective vita
min-containing compositions in discrete, particulate form
consisting essentially of, in intimate admixture
(a) a fat-soluble vitamin material selected from the
group consisting of vitamins A, D, E and K,
3,957,105
16
15
about 1.0 part to about 3.0 parts by weight for each
(b) a hydrophilic carrier for said vitamin material
which is a polysaccharide produced by the controlled
and catalyzed polymerization of special corn sugars,
part by Weight of said (a), and said (d) comprising
from about 0.5% to about 12.0% of the total Weight
of said vitamin-containing composition.
4. Process for producing stable and biologically avail
able and effective vitamin-containing compositions in
discrete particulate form consisting essentially of mixing
said polysaccharide characterized by being water
soluble and organic solvent insoluble, having a pH
of not less than 3.5 when in the form of a 10%
aqueous solution and a viscosity of 20 to 100 poises
at 70° F. when in the form of a 40% aqueous solu
a solvent solution consisting essentially of zein and from
about 2 to about 6 parts by Weight, for each part by
10 weight of said zein, of an organic solvent with a mixture
consisting essentially of a fat-soluble vitamin material
taining composition in a ratio of from about 0.5
selected from the group consisting of vitamins A, D, E
part to about 1.5 parts by weight for each part by
and K and, for each part by weight of said vitamin ma
weight of said (a) and said (0) being present in
terial, a ratio of from about 0.5 to about 1.5 parts by
said vitamin-containing composition in a ratio of
weight of a hydrophilic carrier for said vitamin material
from about 1.0 part to about 3.0 parts by weight for
which is a polysaccharide produced by the controlled and
g each part by weight of said (a).
catalyzed polymerization of special corn sugars, said poly
2. Stable and biologically available and effective vita
saccharide characterized by being water soluble and or
min-containing compositions in discrete, particulate form
ganic solvent insoluble, having a pH of not less than 3.5
consisting essentially of, in intimate admixture
when in the form of a 10% aqueous solution and a
(a) a fat-soluble vitamin material selected from the
viscosity of 20 to 100 poises at 70° F. when in the form
group consisting of vitamins A, D, E and K,
of a 40% aqueous solution, and subsequently removing
(b) a hydrophilic carrier for said vitamin material
tion, and
(c) zein, said (b) being present in said vitamin-con
which is a polysaccharide produced by the controlled
vand catalyzed polymerization of special corn sugars,
said polysaccharide characterized by being water
soluble and organic solvent insoluble, having a pH
the solvent therefrom, said zein being present in the sys
of not less than 3.5 when in the form of a 10%
aqueous solution and a viscosity of 20 to 100 poises
at 70° F. when in the form of a 40% aqueous
5. The process of claim 4 wherein methanol is used as
the solvent.
tem in a ratio of from about 1.0 to about 3.0 parts by
weight for each part by weight of the vitamin material
present.
6. Process for producing stable and biologically avail
able and e?ective vitamin-containing compositions in dis
crete particulate form consisting essentially of mixing a
solvent solution consisting essentially of zein and from
about 2 to about ‘6 parts by weight, for each part by
solution
(0) zein, and
(d) an effective edible antioxidant, said ([2) being
present in said vitamin-containing composition in a
ratio of from about 0.5 part to about 1.5 parts by
weight of said zein, of an organic solvent with a mixture
consisting essentially of a fat-soluble vitamin material
weight for each part by weight of said (a), said (0)
being present in said vitamin-containing composi
selected from the group consisting of vitamins A, D, E
and K and, for each part by Weight of said vitamin ma
terial, a ratio of from about 0.5 to about 1.5 parts by
tion in a ratio of from about 1.0 part to about 3.0
parts by weight for each part by weight of said (a),
weight of a hydrophilic carrier for said vitamin material
"and said (d) comprising from about 0.5% to about
12.0% of the total weight of said composition.
3. Stable and biologically available and effective vita
which is a polysaccharide produced by the controlled
and catalyzed polymerization of special corn sugars, said
polysaccharide characterized by being water soluble and
organic solvent insoluble, having a pH of not less than
min-containing compositions in discrete, particulate form
consisting essentially of, in intimate admixture
(a) a fat-soluble vitamin material selected from the
3.5 when in the form of a 10% aqueous solution and a
group consisting of vitamins A, D, E and K,
(b) a hydrophilic carrier for said vitamin material
which is a polysaccharide produced by the controlled
and catalyzed polymerization of special corn sugars,
said polysaccharide characterized by being water
soluble and organic solvent insoluble, having a pH
viscosity of 20 to 100 poises ‘at 70° F. when in the form
of a 40% aqueous solution, and an effective edible anti
oxidant, said antioxidant comprising from about 0.5%
to about 12.0% of the total weight of the composition,
and subsequently removing the solvent therefrom, said
zein being present in the system in a ratio of from about
1.0 to about 3.0 parts by weight for each part by weight
of not less than 3.5 when in the form of a 10%
aqueous solution and a viscosity of 20 to 100 poises
at 70° F. when in the form of a 40% aqueous
solution,
(c) zein, and
of the vitamin material present.
55
(d) an effective edible antioxidant selected from the
group consisting of butylated hydroxy toluene, bu
tylated hydroxy anisole, ascorbyl palmitate and mix
tures'thereof, said (b) being present in said vitamin
containing composition in a ratio of from about 0.5 60
part to about 1.5 parts by weight for each part by
weight of said (a), said (0) being present in said
vitamin-containing composition in a ratio of from
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,540,253
2,777,797
2,798,838
Gakenheimer __________ __ Feb. 6, 1951
Hochberg ____________ __ Jan. 15, 1957
Robinson _____________ __ July 9, 1957
OTHER REFERENCES
Winters: J. of Am. Pharm. Ass’n. (Sci. Ed.), vol. 47,
No. 8, August 1958, pages 608 and 609.
Cosler: Chem. Abst., vol. 52, 1958, page 17559g.
UNITED STATES PATENT OFFICE
‘CERTIFICATE OF CORRECTION
Patent Non 3iO67nl05
December 1iV 1962
Herman Do Ratish et alo
It is hereby certified that error appears in the above numbered pat
ent requiring correction and that the said Letters Patent should read as
corrected below.
Column 1U line 29a for "'ecective" read ~~ effective -I—;
column .2V line 44LW for "obtatined" read ~-— obtained ~—; line
67, for "at" read —~ as —=—~; column 3g line 50U for "Corn
Products 00°” read w Corn Products Sales C0D -~~; column 40
line 55a for "carier‘" read -~ carrier ew; column 10V line
37?, for “5800" read
5880 We; column 140 line 65V after
"fish"
we‘,
insert
-m
liver
Signed and‘ sealed this 17th day of December 1963B
(SEAL)
Attest:
EDEIVIN L, REYNOLDS
ERNEST W‘D SWIDER
Attesting Officer
AC H1 $31!; Commissioner of Patents